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At least 199 records · Page 11

Extended Analytic Device Optimization Employing Asymptotic Expansion

Analytic optimization of a thermoelectric junction often introduces several simplifying assumptionsincluding constant material properties, fixed known hot and cold shoe temperatures, and thermallyinsulated leg sides. In fact all of these simplifications will have an effect on device performance,ranging from negligible to significant depending on conditions. Numerical methods, such as FiniteElement Analysis or iterative techniques, are often used to perform more detailed analysis andaccount for these simplifications. While numerical methods may stand as a suitable solution scheme,they are weak in gaining physical understanding and only serve to optimize through iterativesearching techniques. Analytic and asymptotic expansion techniques can be used to solve thegoverning system of thermoelectric differential equations with fewer or less severe assumptionsthan the classic case. Analytic methods can provide meaningful closed form solutions and generatebetter physical understanding of the conditions for when simplifying assumptions may be valid.In obtaining the analytic solutions a set of dimensionless parameters, which characterize allthermoelectric couples, is formulated and provide the limiting cases for validating assumptions.Presentation includes optimization of both classic rectangular couples as well as practically andtheoretically interesting cylindrical couples using optimization parameters physically meaningful toa cylindrical couple. Solutions incorporate the physical behavior for i) thermal resistance of hot andcold shoes, ii) variable material properties with temperature, and iii) lateral heat transfer through legsides.

Thermoelectric Generators↗

Seebeck Coefficient Measurement and Its Narrow Band Model Interpretation in FeTe{sub 0.5}Se{sub 0.5} Superconductor

We have measured Seebeck coefficient (S) of FeTe{sub 0.5}Se{sub 0.5} superconducting sample from 10 to 300 K. The variation of Seebeck coefficient with temperature of this system was found to be very anomalous, and the overall experimental observation of the S(T) was studied in the outline of a narrow-band model. In high-temperature region, the Seebeck coefficient is almost independent of temperature. Further, from the study of high-temperature magnitude of S, sample undergoes a change in sign in the Seebeck coefficient, wherein, appearance of a negative peak around 22 K and subsequently, its Seebeck coefficient goes to zero in the superconducting transition temperature regime around 11 to 13 K. It is revealed that the bandwidth and a small asymmetry involved in narrow bands give a realistic explanation to the anomalous temperature dependence of Seebeck coefficient of FeTe{sub 0.5}Se{sub 0.5} system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Influence of rare-earth elements doping on thermoelectric properties of Ca{sub 0.98}Dy{sub 0.02}MnO{sub 3} at high temperature

Ca{sub 0.98}Dy{sub 0.02}MnO{sub 3} and Ca{sub 0.96}Dy{sub 0.02}Re{sub 0.02}MnO{sub 3} (Re=La, Pr, Sm, Eu, Ho, and Yb) have been synthesized by the solid state reaction method. Samples with relative densities all over 96% have been obtained. Thermoelectric properties are evaluated between 300 and 1000 K. The electrical resistivity shows a typical metal-like conductivity behavior, and at high temperature, 973 K, decreases from 36.1 mΩ cm for Ca{sub 0.98}Dy{sub 0.02}MnO{sub 3} to 8.6 mΩ cm for Ca{sub 0.96}Dy{sub 0.02}Yb{sub 0.02}MnO{sub 3}. Both the absolute values of Seebeck coefficient and thermal conductivity are reduced by the introduction of second rare-earth element. The highest power factor of 415 μW/(K{sup 2}m) is obtained for Ca{sub 0.96}Dy{sub 0.02}Yb{sub 0.02}MnO{sub 3} sample, resulting in the highest dimensionless figure of merit (ZT) 0.25 at 973 K. This value shows an improvement of 144% compared with that of Ca{sub 0.98}Dy{sub 0.02}MnO{sub 3} ceramics at the same temperature. - Graphical abstract: The Ca{sub 0.96}Dy{sub 0.02}Re{sub 0.02}MnO{sub 3} (Re=La, Pr, …, Yb) were prepared by solid state reaction. Highest ZT value obtained is 0.25 at 973 K for Re=Yb, which shows 144% improvement compared with Ca{sub 0.98}Dy{sub 0.02}MnO{sub 3}. - Highlights: • Ca{sub 0.96}Dy{sub 0.02}Re{sub 0.02}MnO{sub 3} (Re=La, Pr, …, Yb) are produced by solid state reaction. • Lowest resistivity is obtained due to the highest carrier mobility for Re=Yb. • Highest power factor obtained is 415 μW/(K{sup 2}m) at 973 K for Re=Yb. • Highest ZT value obtained is 0.25 at 973 K for Ca{sub 0.96}Dy{sub 0.02}Yb{sub 0.02}MnO{sub 3} sample.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thermoelectric properties of Fe and Al double substituted MnSi{sub γ} (γ~1.73)

Two series of Fe and Al double substituted MnSi{sub γ} chimney ladders with a nominal valence electron count, VEC=14 per transition metal were prepared (γ=1.75). Simultaneous replacement of Mn with Fe and Si with Al yielded the Mn{sub 1−x}Fe{sub x}Si{sub 1.75−x}Al{sub x} series while the second Mn{sub 1−x}Fe{sub x}Si{sub 1.75–1.75x}Al{sub 2x} series follows the pseudo-binary between MnSi{sub 1.75} and FeAl{sub 2}. Scanning electron microscopy and elemental mapping revealed that ~60% of the nominal Al content ends up in the product with the remainder lost to sublimation, and that up to 7% Al can be substituted in the main group sublattice. Profile analysis of X-ray powder diffraction data revealed gradual changes in the cell metrics, consistent with the simultaneous substitution of Fe and Al in a fixed ratio. All samples are p-type with VEC≈13.95 from the structural data and ~1×10{sup 21} holes cm{sup −3} from variable temperature Seebeck measurements. The substituted samples have lower electrical resistivities (ρ{sub 300} {sub K}=2–5 mΩ cm) due to an improved microstructure. This leads to increased thermoelectric power factors (largest S{sup 2}/ρ=1.95 mW m{sup −1} K{sup −2}) compared to MnSi{sub γ}. The thermal conductivity for the Mn{sub 0.95}Fe{sub 0.05}Si{sub 1.66}Al{sub 0.1} sample is 2.7 W m{sup −1} K{sup −1} between 300 and 800 K, and is comparable to literature data for the parent material. - Graphical abstract: The crystal structure, microstructure and thermoelectric properties of Fe and Al double substituted MnSi{sub γ} (γ~1.73) have been investigated. - Highlights: • Up to 7% Al can be substituted in MnSi{sub γ} when co-doped with Fe. • Improved microstructure and reduced electrical resistivities for Al substituted samples. • Largest power factor 1.95 mW m{sup −1} K{sup −2} and best estimated ZT=0.5.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancement of redox- and phase-stability of thermoelectric CaMnO{sub 3−δ} by substitution

Redox Reactivity and structural phase transitions have a major impact on transport and me-chemical properties of thermoelectric CaMnO{sub 3−δ}. In this study series of Ca{sub 1−x}A{sub x}Mn{sub 1−y}B{sub y}O{sub 3−δ} (0≤x,y≤0.8) compounds, each with A-site (Dy{sup 3+}, Yb{sup 3+}) or B-site (Nb{sup 5+}, Ta{sup 5+} and Mo{sup 6+}, W{sup 6+}) substitution, were synthesized and crystallographically analyzed. It was found that the high-temperature oxygen content is widely independent from the substituent. Subsequently, with increasing temperature the differences in the Seebeck coefficient vanish above 1200 K. With increasing substitution the orthorhombic distortion of the perovskite-like phase increases. The orthorhombic distortion and the upper temperature limit of the stability of the orthorhombic crystal structure show an almost linear dependency. Accordingly, the mechanical stability of all-oxides thermoelectric converters at temperatures exceeding 1000 K will be increased employing materials with high substitution level and substituents inducing a high orthorhombic distortion. - Graphical abstract: Thermoelectric n-type CaMn{sub 0.98}W{sub 0.02}O{sub 3−δ}—Transport properties and expansion coefficient of: Oxygen loss (green region) and upper stability limit of the orthorhombic phase (yellow region) strongly affect the transport properties. Both features also cause lattice expansion, which leads to cracking of thermoelectric all-oxide converters. We report how the upper limit for application can be shifted to even higher temperatures. - Highlights: • Level of Mn{sup 3+} at RT determines reduction behavior of Ca{sub 1−x}A{sub x}Mn{sub 1−y}B{sub y}O{sub 3−δ} at HT. • Differences in Seebeck coefficient vanish at T>1200 K independent from substitution. • Substitution increases orthorhombicity of Ca{sub 1−x}A{sub x}Mn{sub 1−y}B{sub y}O{sub 3−δ}. • Linear dependence of orthorhombicity and phase stability. • Design guidelines for increase of mechanical stability of all-oxide converters.

36 MATERIALS SCIENCE↗

High temperature transport properties of co-substituted Ca{sub 1−x}Ln{sub x}Mn{sub 1−x}Nb{sub x}O{sub 3} (Ln = Yb, Lu; 0.02 ≤ x ≤ 0.08)

Highlights: • The thermoelectric Ca{sub 1−x}Ln{sub x}Mn{sub 1−x}Nb{sub x}O{sub 3} (Ln = Yb, Lu) perovskite are prepared by solid state reaction. • The high temperature transport properties are explored. • The co-substituted Ca{sub 1−x}Ln{sub x}Mn{sub 1−x}Nb{sub x}O{sub 3} shows non-metal-like temperature dependence of resistivity. • The Seebeck coefficient of Ca{sub 1−x}Ln{sub x}Mn{sub 1−x}Nb{sub x}O{sub 3} exhibits metallic nature. • The puzzling transport phenomenon is originated from oxygen vacancy related defect centres. - Abstract: The co-substituted Ca{sub 1−x}Ln{sub x}Mn{sub 1−x}Nb{sub x}O{sub 3} (Ln = Yb, Lu; 0.02 ≤ x ≤ 0.08) are synthesized by solid-state reaction and the electronic transport properties are investigated. Rietveld refinement confirms the formation of single phase orthorhombic structure with gradual increase of cell parameters with doping level. The electronic transport properties such as Seebeck coefficient and electrical resistivity decrease with increasing the dopant concentration for both the co-substituted compositions. All the compositions of Ca{sub 1−x}Ln{sub x}Mn{sub 1−x}Nb{sub x}O{sub 3} show nonmetal-like temperature dependence of resistivity; whereas metal-like temperature dependence of thermopower. This inconsistency is explained by the formation of oxygen vacancy associated defect centres that originates from partial reduction of Mn{sup 4+} to Mn{sup 3+} due to co-substitution. The defect centres act as extrinsic carriers and cause additional contribution to the entropy of the system, leading to increase of Seebeck coefficient as a function of temperature. The transport mechanism of charge carriers is explained in the framework of Mott’s small polaron hopping mechanism.

36 MATERIALS SCIENCE↗

Stabilization of high-performance rock-salt LiMnSbTe3 thermoelectrics with embedded van der Waals-like gaps

Rock-salt-structured compounds like lead chalcogenides are promising thermoelectrics, as their high symmetry, strong anharmonicity, and favorable phase behavior collectively lead to high performance by enabling large power factors and ultralow thermal conductivity. Here, we report LiMnSbTe 3 , a new rock-salt semiconductor stabilized through targeted chemical design by combining hexagonal MnTe with cubic LiSbTe 2 . Embedded in the highsymmetry matrix, van der Waals-like gaps form due to Sb 2 Te 3 nanoscale segregation, which acts as effective phonon-scattering centers, leading to a low lattice thermal conductivity of 0.37Wm- 1 K -1 at 873 K with alloy scattering from disordered cations. The ordered local structure of Sb2Te 3 -type vdW-like gaps and the cross-gap interaction facilitate the carrier transport. Aided by energyconverged valence bands and a paramagnon drag effect, high Seebeck coefficients and enhanced power factor can be achieved, leading to a high ZT of 1.2 at 873 K. Furthermore, introducing Mn deficiency increases ZT to 1.5, highlighting the potential for higher performance through optimized doping or alloying. A segmented single-leg thermoelectric module achieves an output power density of 0.52 Wcm -2 and an efficiency of 8.7% under ΔT of 478 K, further demonstrating its promising thermoelectric applications.

42 ENGINEERING↗

Structural and thermoelectric properties of BaRCo{sub 4}O{sub 7} (R = Dy, Ho, Er, Tm, Yb, and Lu)

The structure and thermoelectric properties of a series of barium lanthanide cobaltites, BaRCo{sub 4}O{sub 7} (R = Dy, Ho, Er, Tm, Yb, and Lu), which were prepared using the spark plasma synthesis technique, have been investigated. The space group of these compounds was re-determined and confirmed to be P31c instead of the reported P6{sub 3}mc. The lattice parameters a and c range from 6.26279(2) Angst to 6.31181(6) Angst , and from 10.22468(6) Angst to 10.24446(15) Angst for R = Lu to Dy, respectively. The crystal structure of BaRCo{sub 4}O{sub 7} is built up from Kagome sheets of CoO{sub 4} tetrahedra, linked by triangular layers of CoO{sub 4} tetrahedra. The values of figure of merit (ZT) of the BaRCo{sub 4}O{sub 7} samples were determined to be around 0.02 at 800 K. X-ray diffraction patterns of these samples have been determined and submitted to the Powder Diffraction File.

36 MATERIALS SCIENCE↗

Anomalously high thermoelectric power factor in epitaxial ScN thin films

Thermoelectric properties of ScN thin films grown by reactive magnetron sputtering on Al{sub 2}O{sub 3}(0001) wafers are reported. X-ray diffraction and elastic recoil detection analyses show that the composition of the films is close to stoichiometry with trace amounts ({approx}1 at. % in total) of C, O, and F. We found that the ScN thin-film exhibits a rather low electrical resistivity of {approx}2.94 {mu}{Omega}m, while its Seebeck coefficient is approximately {approx}-86 {mu}V/K at 800 K, yielding a power factor of {approx}2.5 x 10{sup -3} W/mK{sup 2}. This value is anomalously high for common transition-metal nitrides.

36 MATERIALS SCIENCE↗

Tunning of microstructure and thermoelectric properties of Ca{sub 3}Co{sub 4}O{sub 9} ceramics by high-magnetic-field sintering

The structural, magnetic, electrical, and thermal transport properties of Ca{sub 3}Co{sub 4}O{sub 9} ceramics sintered under high magnetic field were investigated. Crystal grain texturing and densification were achieved through cold-pressing and high-magnetic-field sintering techniques. The c-axis of the layered crystal grain was partly oriented along the c-axis of the pressed samples via a cold-pressing technique, and the degree of orientation was further increased while applying the magnetic field in the sample sintering progress. The easy magnetization axis of Ca{sub 3}Co{sub 4}O{sub 9} polycrystalline ceramics was found to be the c-axis. The room-temperature resistivity along the ab-plane of the sample sintered under 8 T magnetic field was about 30% smaller than that of the sample sintered without magnetic field, and the Seebeck coefficient of the former reached 177.7 {mu}V/K at the room temperature, which is about 50% larger than that of the latter. Consequently, for the sample sintered at 8 T magnetic field, the power factor along the ab-plane was enhanced by about 1.8 times compared to the sample without magnetic field sintering. The obtained result is suggested to originate from the variations of the carrier mobility and spin-orbital degeneracy due to high-magnetic-field sintering in the progress of the sample preparation.

36 MATERIALS SCIENCE↗

Thermoelectric properties of Ni-doped CeFe4Sb12 skutterudites

We have prepared Ni-doped p-type skutterudites Ce{sub y}Fe{sub 4-x}Ni{sub x}Sb{sub 12} and systematically studied their thermoelectric properties. The lattice parameters of these skutterudites are found to be sensitive to both the Ni content and Ce-filling fraction. With increasing Ni content, the electrical conductivity decreases and the Seebeck coefficient increases, consistent with the expected decrease in hole concentration due to the extra electrons introduced by Ni. All Ni-doped samples possess similar band gap values. We also find that the Ni-doped Ce{sub y}Fe{sub 4-x}Ni{sub x}Sb{sub 12} system has electrical transport properties similar to those of Co-doped Ce{sub y}Fe{sub 4-x}Co{sub x}Sb{sub 12} system at a similar nominal hole concentration based on a simple charge counting. We do, however, find a pronounced bi-polar phenomenon in thermal conductivity that rapidly increases for Ni-doped samples when temperature is above 600 K. Importantly, Ni-doped samples have higher dimensionless thermoelectric figures of merit values than CeFe{sub 4}Sb{sub 12} over the entire temperature range measured. Therefore, Ni doping is useful for improving the energy conversion efficiency in applications.

36 MATERIALS SCIENCE↗

Thermoelectric properties of epitaxial TbAs:InGaAs nanocomposites

InGaAs lattice-matched to InP was grown by molecular beam epitaxy with randomly distributed TbAs nanoparticles for thermoelectric power generation applications. TbAs:InGaAs is expected to have a large thermoelectric figure of merit, ZT, particularly at high temperatures, owing to energy band alignment between the nanoparticles and their surrounding matrix. Here, the room temperature thermoelectric properties were measured as a function of TbAs concentration, revealing a maximum thermoelectric power factor of 2.38 W/mK{sup 2} and ZT of 0.19 with 0.2% TbAs. Trends in the thermoelectric properties closely resemble those found in comparable ErAs:InGaAs nanocomposite materials. However, nanoparticles were not observed by scanning transmission electron microscopy in the highest ZT TbAs:InGaAs sample, unlike the highest ZT ErAs:InGaAs sample (0.2% ErAs) and two higher concentration TbAs:InGaAs samples examined. Consistent with expectations concerning the positioning of the Fermi level in these materials, ZT was enhanced by TbAs incorporation largely due to a high Seebeck coefficient, whereas ErAs provided InGaAs with higher conductivity but a lower Seebeck coefficient than that of TbAs:InGaAs. Thermal conductivity was reduced significantly from that of intrinsic thin-film InGaAs only with TbAs concentrations greater than {approx}1.7%.

36 MATERIALS SCIENCE↗

Development of the method for the preparation of Mg{sub 2}Si by SPS technique

The aim of the study was to develop a fast and simple method for preparation of polycrystalline Mg{sub 2}Si. For this purpose a Spark Plasma Sintering (SPS) method was used and synthesis conditions were adjusted in such a manner that no excess Mg was required. Materials were synthesized by the direct reaction of Mg and Si raw powders. To determine the phase and chemical composition, the fabricated samples were studied by X-ray diffraction and SEM microscopy coupled with EDX chemical analysis. Thermoelectric properties of samples (thermal conductivity, electrical conductivity and Seebeck coefficient) were measured all over temperature range of 300-650 K. The analysis by the scanning thermoelectric microprobe (STM) shows that samples have uniform distribution of Seebeck coefficient with mean value of about -405 {mu}VK{sup -1} and standard deviation of 94 {mu}VK{sup -1}. Prepared materials have intrinsic band gap of 0.45 eV and thermal conductivity {lambda}= 7.5 Wm{sup -1}K{sup -1} at room temperature.

36 MATERIALS SCIENCE↗

Anisotropy analysis of thermoelectric properties of Bi{sub 2}Te{sub 2.9}Se{sub 0.1} prepared by SPS method

The n-type Bi{sub 2}Te{sub 2.9}Se{sub 0.1} materials were synthesized by the direct fusion technique. The polycrystalline samples were fabricated by the uniaxial pressing of powders in spark plasma sintering (SPS) apparatus. The materials were subjected to the heat treatment in H{sub 2}-Ar atmosphere at 470 K for 24 h. The influence of preparation conditions on the anisotropy of electrical and thermal properties was thoroughly studied for the direction perpendicular and parallel to the pressing force. The microstructure and the chemical composition of both types of samples were examined using a scanning microscope (SEM) equipped with an X-ray energy dispersion detector (EDX). The XRD method was applied for the phase analysis of materials, as well as, for determination of preferred orientation of Bi{sub 2}Te{sub 2.9}Se{sub 0.1} grains. The Seebeck coefficient distribution was studied by the scanning thermoelectric microprobe (STM). Temperature dependences of thermoelectric properties (thermal and electrical conductivities, Seebeck coefficient) were measured in the temperature from 300 K to 550 K. The statistical analysis of results has shown strong influence of pressing force direction both on structural and transport properties. The applied heat treatment of materials significantly improves their thermoelectric figure of merit. Particularly, it was found that annealing in H2-Ar atmosphere leads to enhancement of the ZT three times up to {approx}0.7 at 370 K in perpendicular direction to the pressing force.

36 MATERIALS SCIENCE↗

Zn migration during spark plasma sintering of thermoelectric Zn{sub 4}Sb{sub 3}

The phase homogeneity of spark plasma sintered thermoelectric Zn{sub 4}Sb{sub 3} pellets along the pressing direction has been studied by potential Seebeck microprobe scanning and spatially resolved x-ray diffraction. Significant variations in the Seebeck coefficient reflect presence of different crystalline phases. The emergence of the ZnSb phase at the bottom of the pellet and metallic Zn impurity at the top explains the variation in the Seebeck coefficients. Quantitative phase distributions along the pressing axis were determined from the Rietveld refinements of spatially resolved x-ray diffraction patterns. These reveal a migration of highly mobilized Zn atoms under the direct current applied during spark plasma sintering.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

An apparatus for concurrent measurement of thermoelectric material parameters

We describe an apparatus which concurrently and independently measures the parameters determining thermoelectric material conversion efficiency: the Seebeck coefficient, thermal conductivity, and electrical resistivity. The apparatus is designed to characterize thermoelectric materials which are technologically relevant for waste heat energy conversion, and may operate from room temperature to 400 Degree-Sign C. It is configured so the heat flux is axially confined along two boron nitride rods of known thermal conductance. The Seebeck coefficient and thermal conductivity are obtained in steady-state using a differential technique, while the electrical resistivity is obtained using a four-point lock-in amplification method. Measurements on the newly developed NIST Seebeck standard reference material are presented in the temperature range from 50 Degree-Sign C to 250 Degree-Sign C.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗